IOSR Journal of Applied Chemistry (IOSR-JAC)

e-ISSN: 2278-5736.Volume 8, Issue 3 Ver. I. (Mar. 2015), PP 34-38

www.iosrjournals.org

Triethanolamine (TEA) As Flow Improver For Heavy Crude Oils

Caleb Abiodun Popoola1*, Jerome Adekunle Ayo1, Olajide Emmanuel Adedeji1
and Ogungbemi Akinleye2
1

(Food Science and Technology Department,Faculty of Agric and Life Sciences, Federal University Wukari,
P.M.B. 1020, Wukari, Taraba State, Nigeria)

(National Centre for Technology Management (NACETEM), South-South Office, Amassoma, Bayelsa State, Nigeria).

Abstract: The production of crude oils is normally in remotes areas and pipelines are the most energy efficient
way of transporting it. The crude oils being very viscous on extraction have to go through some processing to
enable them to be transported by pipeline. Fresh crude oil is relatively mobile; however at lower temperatures
when it has to be transported long distances through pipelines, it gradually becomes thicker and sluggish
hampering its flow properties by forming crystals of wax on its wall and making it difficult to pump. Some heavy
crude oils are characterized by high viscosity, high content of asphaltenes, low quantity of paraffin components
and appreciable amounts of sulphur. Therefore, it is important to minimize the viscosity of the heavy crude oil.
One well-known method of alleviating the problem is to treat the crude oil with wax crystal modifier. There are
several options available including chemical additives such as flow improvers, viscosity reducer, and pour point
depressants (PPDs). This work involves the evaluation of triethanolamine (TEA) as pour point depressant and
flow improver by changing the feed ratios. Niger-Delta crude oil was used to evaluate the efficiency of
triethanolamine (TEA) as additive through measurements of pour point and viscosity of treated and untreated
crude oil. Triethanolamine (TEA) interferes in the wax crystallization process thus modifying the crystal
structure of the paraffin present in the crude oil resulting in lowering pour point and viscosity of the crude oil.
Keywords: Pour point, Pour point depressants, Viscosity, Flow improver, Asphaltenes, Triethanolamine
(TEA),

I.

Introduction

Crude oils are complex hydrocarbon mixtures containing non-polar n-paraffins and polar components
such as asphaltenes. Heavy oil is defined as petroleum which has a density equal or lower than 20 API, but if
petroleum has 10 API or less, it is considered as extra heavy oil or bitumen, which is denser than water (Khan,
1996). According to some estimates from Inter Energy Agency (IEA), as reported by Atta et al. (2013), heavy
oil represents at least half of the recoverable oil resources of the world. Crude oil having high wax content
causes many problems during production, storage and transportation. One of the main problems is the
crystallization and deposition of paraffin wax crystals in the flow line which is more severe in winter (Soni et
al., 2005). At low temperature, as the crude oil flows through these pipelines, crystals of wax may be formed on
its walls. These wax crystals then grow in size until the whole inner wall is covered with wax layers; this result
into the reduction of flow and extra burden on the pumping system. As the wax thickness increases, pressure
across the pipe needs to be increased to maintain a constant flow rate, thus the power requirement to transport
the crude oil also increases. Another major problem during the handling of waxy crude oil as reported by
Egyptian Petroleum Research Institute (2006), is restarting of the pipeline after prolong shut down period; the
cooled oil slowly develops gel structure which results into high yield stress.
The wax crystals deposition leads to higher viscosity of crude oil and reduction of the effective crosssectional area of the pipe (Anons, 2013). Solving the wax deposition problems is therefore an economically
beneficial target which can be highly achieved by introducing chemical additive to the crude oil in order to
reduce its viscosity and pour point temperature. Although crude oil treatment with chemical additives is not the
only known solution for inhibition of wax deposition, it remains the preferred solution over other options like
pigging, heating and biological treatments (Atta et al., 2013). The pour point and rheological properties of the
crude oil can be improved by adding requisite amount of flow improver. Johnston et al. (2009) described flow
improvers or pour point depressants (also known as drag-reducing agents, DRAs) as long-chain, ultra-highmolecular-weight that reduces the level of turbulence in fluid streams. They are generally used to lower the pour
point, viscosity, yield stress of the crude oil and improve the fluidity of waxy crude oil, thereby reduce the extra
pumping cost.
According to Johnston et al. (2009), typical molecular weights for drag-reducing polymers are greater
than 5million and when using parts per million (ppm), concentration level in the fluid stream, drag-reducing
polymers interact with the fluid molecules that reduce the formation and propagation of turbulent eddies. It was
explained that this decreases deviations in velocity relative to the bulk flow of fluid, causing the hydraulic
DOI: 10.9790/5736-08313438

www.iosrjournals.org

34 |Page

Triethanolamine (TEA) As Flow Improver For Heavy Crude Oils

energy to be more focused on moving the fluid stream down the pipeline rather than in a chaotic random motion
and the reduced frictional pressure losses enable pipeline operators to lower operating pressure or increase the
rate of fluid flow.
Viscosity is the ratio of shear stress to shear rate. It is defined empirically as the resistance offered by
fluid to flow at a given temperature. An increase in temperature of the oil lowers the viscosity, while a decrease
in temperature increases the viscosity. The viscosity-temperature relationship must be established accurately in
order to determine pump ability of the oil.
Pour point is the temperature at which the crude oil is just able to flow and below which there is
complete absence of flow in it. It represents the lowest temperature at which the crude oil can be stored or
handled without congealing in the tanks or pipelines.
According to Ajienka (1997), pour point is usually 100C 200C lower than cloud point. Cloud point is
defined as the temperature at which the first wax crystal separates out from crude oil. Below the cloud point,
crude oil containing high amount of wax possesses high pour point and exhibit non-Newtonian viscosity
behavior. The wax appearance temperature (WAT) and the pour point temperature (PPT) are good pointers to
the temperature regime, in which a waxy crude oil is expected to start to show non-Newtonian behavior as
reported by Taiwo, et al. (2012). As temperature decreases, the abrupt rise in crude oil viscosity depends upon
the quantity as well as type of wax present in it.
Soni et al. (2006) discussed the synthesis and evaluation of polymeric additives as pour point
depressants and flow improvers for crude oil. They studied the rheological properties of crude oil (with or
without additives) in terms of shear rate, shear stress, yield stress and viscosity and listed three main
characteristics for any additive to behave as flow improver should have, which are:
(i) A wax like paraffin part, typically mixture of linear alkyl chain of 14 to 25 carbon atoms long that cocrystallize with oils wax forming component.
(ii) A polar component typically acrylates or acetates that limits the degree of co-crystallization.
(iii) Polymers that when adsorbed on the growing wax crystals stearically hindered their growth, resulting into
small crystal.
It should be noted that any additive as a pour point depressant may be ineffective to reduce viscosity,
yield stress and enhance the flow. The following factors according to Soni et al. (2006) play an important role in
the efficiency of flow improvers and pour point depressants
a number of pendant of alkyl side chains and the length and distance between them.
the solubility of the additives in crude oil which depends on their average molecular weights.
amorphous and crystalline parts of additive are very important in determining its efficiency
physical and chemical stability of additive.
if additive is copolymer then monomer to monomer ration should be taken into consideration.
Triethanolamine (TEA), co-polymer, satisfies most of these requirements. TEA is a part of a class of
organic compounds called ethanolamines; combines the properties of amines and alcohols. It is a viscous
organic compound that is both tertiary amine and triol (with three alcohol groups) (IARC, 2012). It is a weak
base, colourless and has a mild ammoniacal odour. TEA has molecular formular C 6H15NO3 with relative
molecular mass of 149.19, boiling point of 335.4 0C, melting point of 20.50C, density of 1.1242g/cm3 at 200C,
vapour pressure less than 1.3pa at 200C. It is miscible with water, acetone, ethanol and methanol; soluble in
chloroform and slightly soluble in benzene, diethyl ether and lignans (Lide & Milne, 1996).
TEA is produced from the reaction of ethylene oxide with aqueous ammonia. It is used primarily as an
emulsifier and surfactant. It is a common ingredient in formulations used for both industrial and consumer
products. The triethanolamine neutralizes fatty acids, adjusts and buffers the PH and solubilises oil and other
ingredients that are not completely soluble in water. It reacts with acids to form salt and soap and is also used as
flow improver additive in crude oil (DOW, 2010). Viscosity reduction is imminent to improve mobility of heavy
crude oils; doping with solvent like triethanolamine (TEA), which keeps the wax in solution, is essential in
ensuring oil mobility. Based on evaluation of preliminary studies, Taiwo et al. (2003), showed triethanolamine
(TEA) to be a very good wax deposition inhibitor.

II.

Experimental Methods

Evaluation tests of flow Improvers

Effectiveness of triethanolamine (TEA) as flow improver for the heavy crude oils was determined
through the pour point test and kinematic viscosity.

DOI: 10.9790/5736-08313438

www.iosrjournals.org

35 |Page

Triethanolamine (TEA) As Flow Improver For Heavy Crude Oils

Experimental Materials
The materials used for this study were: crude oil samples and triethanolamine (TEA). All crude oil
samples used in this study were from Niger-Delta oil field in Nigeria, with density of 847 869 kg/m3 and API
gravity in the range of 24.4 36.5 at 150C. Standard methods were employed in determination of the physical
properties.
Determination of pour points
The equipment used to determine pour points were: a standard pour point test apparatus, a
thermometer, test tubes and heater. The standard pour point was obtained in all cases with the sample generally
heated to about 350C to 400C and then cooled down to its pour point inside the pour point test apparatus. The
sample was checked at regular intervals until flow ceased. If the flow did not occur after 5 seconds when the test
tube was tipped horizontally, the temperature was then taken and recorded to give the pour point.
Determination of Viscosity
The equipment used for viscosity determination includes the following: Viscometer, a water bath, a
thermometer, a thermostat and heater. The viscosity was obtained by following this procedure: the sample was
heated to about 450C to improve the fluidity and then allowed to cool to room temperature. While the sample
cools, the water bath was switched on with thermometer; thermostat was set to room temperature and inserted
into the water bath to regulate the temperature of the water bath. 50ml of the crude oil sample at room
temperature was poured into the viscometer and clasped/fastened onto a metal stand, this was inserted into the
water bath with the stand suspended in the water bath cover. The crude oil, with the aid of a sucker pipette was
sucked to a set mark in the viscometer. The stop clock was started and time at which the crude oil flows from
the upper mark to the lower mark was recorded. The thermostat was set to 35 0C, which automatically starts the
heater in the water bath raising the temperature to 350C. The procedures were repeated for temperature 450C,
550C, and 650C for samples with and without triethanolamine (TEA).

III.

Results and Discussions

Effect of Added Triethanolamine (TEA) on the Viscosity and Pour point of the heavy Crude oil
The viscosity of the pure crude oil sample at different temperature is shown in Table 1, while the effect
of added triethanolamine (TEA) on the viscosity and pour point of the crude oil at different temperatures is
detailed in Table 2 and Table 3 respectively below:
Table 1: Viscosity of Pure Crude oil Sample
Temperature (0C)
Time (sec)
28
35
45
55
65

K. Viscosity (cSt)

1835
381
305
258
222

54.32
11.28
9.03
7.64
6.57

Note: Kinematic viscosity (K) = ct, where c= constant = 0.02959, t = time

Table 2: Viscosity of Crude oil Sample mixed with Different percentage of Triethanolamine (TEA) at
different Temperatures.
Percent. of
Additives(%)

Viscosity
at 280C (cSt)

Viscosity
at 350C (cSt)

Crude Oil
+ 0% TEA

54.32

11.98

9.03

7.64

6.57

Crude Oil
+ 0.05% TEA

17.74

9.32

6.21

5.12

4.20

Crude Oil
+ 0.1% TEA

18.56

9.59

6.30

5.33

4.23

Crude Oil
+ 0.5% TEA

21.31

9.89

6.93

5.39

4.68

Crude Oil
+ 1% TEA

26.17

10.26

7.30

5.92

4.72

Crude Oil
+ 2.5% TEA

31.17

11.19

7.45

6.93

4.89

Crude Oil
+ 5% TEA

34.75

11.72

7.61

6.99

5.08

DOI: 10.9790/5736-08313438

Viscosity
at 450C (cSt)

Viscosity
at 550C (cSt)

www.iosrjournals.org

Viscosity
at 650C (cSt)

36 |Page

Triethanolamine (TEA) As Flow Improver For Heavy Crude Oils

Table 3: Pour point of Crude Oil Sample mixed with Different Percentage of Triethanolamine (TEA)
Percentage of
Additives (%)
Crude Oil + 0% TEA
Crude Oil + 0.05% TEA
Crude Oil + 0.1% TEA
Crude Oil + 0.5% TEA
Crude Oil + 1% TEA
Crude Oil + 2.5% TEA
Crude Oil + 5% TEA

Pour Point
(0C)
32
17
17
17
17
17
17

Figure1: Chart of proportions of TEA in crude oil and its viscosity

Effect of Chemical additive on the crude oil viscosity: Table 2 and Figure 1 show the effect of
triethanolamine (TEA) on the viscosity of crude oil at different temperature. The effect of chemical additive
(TEA) on the viscosity of crude oil was evaluated. Different doses (i.e. 0.05%, 0.1%, 0.5%, 1%, 2.5% and 5%)
were tried at different temperatures to determine the viscosity. As can be seen from Table 2, triethanolamine
(TEA) decreased the viscosity at different temperatures. As volume of added triethanolamine increases, the
viscosity of the crude oil increases and vice versa (Figure 1). This is in line with findings of Soni, et al. 2005, in
which it was observed that crude oil responses differently with the same additive at different doses, as a result of
changes in rheological properties of the crude oil.
The table shows that the molecular weight of the additive plays an important role in affecting the
viscosity of the crude oil. The higher molecular weight polymer imparts higher viscosity. The structure of the
polymer and its solubility in crude oil are also important. The viscosity of the crude oil can be improved by
adding requisite amount of flow improver, the appropriate volume of the additive has to be added for
effectiveness. Triethanolamine (TEA) performs very well at 650C with 0.05% volume and agreed with Taiwo, et
al. 2012, report that triethanolamine (TEA) is a very good wax deposition inhibitor. With 0.05% volume
fraction of triethanolamine (TEA), the shear thinning behavior is enhanced, and the viscosity as well as the pour
point decreases as temperature increases. The reduction of viscosity on the addition of the solvent is due to the
dissolution of paraffin wax, which shows the effectiveness of triethanolamine (TEA).
Effect of Temperature on the crude oil viscosity: Temperature has a strong effect on viscosity and viscous
behavior. The kinematic viscosity decreases considerably with increasing temperature. From Table 2, at high
temperature wax in the crude oil could not agglomerate and form aggregates, hence reducing the oil viscosity.
This is similar to an earlier work of Taiwo, et al. 2012 on waxy crude oil, the apparent viscosity decreases
considerably with increasing temperature. The variation with temperature is attributable to the strong effect of
temperature on the viscosity of wax and asphaltene components in the crude oil. At high temperature, the
ordered structures of these chemical components are destroyed and hence reducing oil viscosity (Khan, 1996).
DOI: 10.9790/5736-08313438

www.iosrjournals.org

37 |Page

Triethanolamine (TEA) As Flow Improver For Heavy Crude Oils

Effect of Temperature on the pour point: The depression in pour point is mainly due to wax crystal
modification. Pour point depressants molecules are adsorbed on the various crystals faces, thereby decreasing
the interlocking forces between two nuclei of wax molecules and deforming the regular crystal growth. The pour
point depressant changes the wax crystal shapes when present in crude oil from thin extensively interlocking
plates to more compact crystals by co-crystallizing with the wax. Table 3 shows the depression in pour point.
Triethanolamine (TEA) reduced the pour point of the crude oil up to 170C from 320C. It can be seen from the
table that triethanolamine (TEA) actively decreased the pour point of the samples and their wax deposition
potentials on doping. The oxygen containing group in the triethanolamine takes the role of inhibiting the growth
waxes and poisoning them by adsorptive surface poisoning mechanism. The waxes then occur in small sized
particles in the crude oil and cannot form net-like structure required for solidification and deposition.

IV.

Conclusion

The resins and asphaltenes present in the crude oil play a significant role on the flow properties of
crude oil. In a search for effective chemical additives for improving the flow properties of crude oil,
triethanolamine (TEA) was synthesized and characterized in the laboratory and its effects on pour point and
rheological properties of the crude oil was investigated. Triethanolamine (TEA) is an effective crude oil pour
point depressant and flow improver. It satisfies most of the requirements to act as a pour point depressant and
flow improver. It has also been shown that temperature has significant effect on pour point and viscosity of
crude oil.

References
[1].
[2].
[3].

[4].
[5].
[6].
[7].
[8].
[9].
[10].
[11].
[12].
[13].
[14].

Ajienka, J.A and Ikoku, C.V. (1997). Waxy Crude Oil handling in Nigeria: Practices, Problems and Prospects. Energy Source.
12(4), 463 478.
Anonymous, (2013). Oilfield Drilling and Exploration Chemicals: Pour Point Depressants. www.constol.co.in/pro_oil_ppd.asp.
(June 23, 2013).
Atta, A.M., El-Ghazawy, R.A., Morsy, F.A., Ali, M.S.A. and Elmorsy, A. (2013). Synthesis and Characterization of Polymeric
additives and their effect on flow properties of waxy Egyptians Crude Oil. Global Journal of Science Frontier Research Chemistry.
13(10), 21 27.
Castro, L.V., Flores, E., and Vazquez, F., (2012). Terpolymers as Flow Improvers for Mexican Crude Oils.
DOW, (2010). Product Safety Assessment: DOW TM Triethanolamine.
Available at: www.dow.com/productsafety/finder.
Egyptian Petroleum Research Institute (2013). Improvement of Crude Oils Flow Properties through the use of Locally Produced
Polymeric Materials.
IARC, (2012). Triethanolamine. IARC Monograph. 77, 381 385.
Johnston, R.L., Lauzon, P.A. and Pierce, J.D. (2009). Increasing Heavy Crude Oil flow through a New Flow Improver Product A
case study. A report by Conocophillips Specialty Products Inc.
Khan, M.R. (1996). Rheological property of heavy oils and heavy oil emulsions. Energy Source.18, 385 391.
Lide, D.R. and Milne, G.W.A. (1996). Properties of Organic Compounds. Version 5.0. Boca Raton. FL. CRC Press.
Soni, H. P. and Bharambe, D.P. (2006). Synthesis and Evaluation of Polymeric Additives as Flow Improvers for Indian Cru de Oil.
Iranian Polymer Journal. 15(12), 943 954. Available online at: http//www.journal.ippi.ac.ir.
Soni, H. P., Bharambe, D.P., Nagar, A., and Kiranbala (2005). Synthesis of Chemical Additives and their effect on Akholjuni
Crude Oil (Gujarat, India). Indian Journal of Chemical Technology. 12, 55 61.
Taiwo, E., Otolorin, J. and Afolabi, T. (2012). Crude Oil Transportation: Nigerian Niger-Delta Waxy Crude. Crude Oil Exploration
in the World;
Prof.
Mohamad Younes (Ed.).
ISSBN:
978-953-51-0379-0.
InTech.
Available
from:
http://www.intechopen.com/books/crude-oil-exploration-in-the-world/crude-oil-transportation-nigerian-niger-delta-waxy-crude-oil.

DOI: 10.9790/5736-08313438

www.iosrjournals.org

38 |Page